US2763609A - Vulcanization of silicone rubber with high energy electrons - Google Patents

Vulcanization of silicone rubber with high energy electrons Download PDF

Info

Publication number
US2763609A
US2763609A US291542A US29154252A US2763609A US 2763609 A US2763609 A US 2763609A US 291542 A US291542 A US 291542A US 29154252 A US29154252 A US 29154252A US 2763609 A US2763609 A US 2763609A
Authority
US
United States
Prior art keywords
convertible
organopolysiloxane
electrons
high energy
vulcanization
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US291542A
Other languages
English (en)
Inventor
Frederick M Lewis
Elliott J Lawton
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority to BE520402D priority Critical patent/BE520402A/xx
Priority to DENDAT1050993D priority patent/DE1050993B/de
Application filed by General Electric Co filed Critical General Electric Co
Priority to US291542A priority patent/US2763609A/en
Priority to GB15194/53A priority patent/GB757024A/en
Priority to FR1080171D priority patent/FR1080171A/fr
Application granted granted Critical
Publication of US2763609A publication Critical patent/US2763609A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C59/00—Surface shaping of articles, e.g. embossing; Apparatus therefor
    • B29C59/16—Surface shaping of articles, e.g. embossing; Apparatus therefor by wave energy or particle radiation, e.g. infrared heating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/10—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation for articles of indefinite length
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C71/00—After-treatment of articles without altering their shape; Apparatus therefor
    • B29C71/04—After-treatment of articles without altering their shape; Apparatus therefor by wave energy or particle radiation, e.g. for curing or vulcanising preformed articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C35/00—Heating, cooling or curing, e.g. crosslinking or vulcanising; Apparatus therefor
    • B29C35/02—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould
    • B29C35/08—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation
    • B29C35/0866—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation
    • B29C2035/0877—Heating or curing, e.g. crosslinking or vulcanizing during moulding, e.g. in a mould by wave energy or particle radiation using particle radiation using electron radiation, e.g. beta-rays
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2083/00—Use of polymers having silicon, with or without sulfur, nitrogen, oxygen, or carbon only, in the main chain, as moulding material
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S264/00—Plastic and nonmetallic article shaping or treating: processes
    • Y10S264/46—Molding using an electrical heat

Definitions

  • This invention relates to the curing or vulcanization of organopolysiloxanes convertible to the solid elastic state. More particularly, the invention is concerned with the curing of the aforesaid organopolysiloxanes by irradiation of the latter with high energy electrons.
  • the vulcanization or curing of organopolysiloxanes to the solid elastic state has been efiected by means of curing agents such as benzoyl peroxide, tertiary butyl perbenzoate, etc., in combination With the application of heat.
  • curing agents such as benzoyl peroxide, tertiary butyl perbenzoate, etc.
  • the use of such curing agents is accompanied by the disadvantage that after the product is converted to the solid, elastic, substantially infusible and insoluble state, the presence of chemical residues of the aforesaid curing agents tends to afi'ect deleteriously some of the properties of the cured product, such as the heat-aging properties, the electrical properties, etc.
  • a still further object is to vulcanize silicone rubber 1 nited States Patent 0 filled with fillers which cannot be satisfactorily cured by the use of the usual chemical curing agents.
  • Another object of the invention is to effect vulcanization of organopolysiloxanes to the solid elastic state in varying degrees of depth which cannot be done by presently known methods.
  • the convertible organopolysiloxane or silicone compositions which may be highly viscous masses, or gummy elastic solids, depending on the state of condensation, the condensing agent employed, the starting organopolysiloxane used to make the convertible organopolysiloxances, etc., will hereinafter be referred to as convertible organopolysiloxane or, more specifically, as convertible methylpolysiloxane.
  • convertible organopolysiloxanes with which the present invention is concerned are well known, for purposes of showing persons skilled in the art the various convertible organopolysiloxanes which may be employed in the practice of the present 2,763,609 Patented Sept.
  • the particular convertible organopolysiloxane used is not critical and may be any one of those described in the foregoing patents and generally obtained by condensing a liquid organopolysiloxane containing an average of from about 1.95 to 2.25, preferably from about 1.98 to about 2.05, silicon-bonded organic groups per silicon atom.
  • the usual condensing agents which may be employed and which are well known in. the art may include, for instance, ferric chloride hexahydrate, phenyl phosphoryl chloride, alkaline condensing agents, such as potassium hydroxide, sodium hydroxide, etc.
  • These convertible organopolysiloxanes generally comprise polymeric diorganosiloxanes which may contain, for example, 2 mol per cent copolymerized monorganosiloxane, for example, copolymerized monomethylsiloxane.
  • polymeric diorganosiloxanes which may contain, for example, 2 mol per cent copolymerized monorganosiloxane, for example, copolymerized monomethylsiloxane.
  • the starting liquid organopolysiloxane from which the convertible organopolysiloxanes are prepared one which contains about 1.999 to 2.01, inclusive, organic groups, for example, methyl groups per silicon atom Where more than about 90 per cent of the silicon atoms in the polysiloxane contain two silicon-bonded dialkyl groups.
  • the starting organopolysiloxanes used to make the convertible organopolysiloxanes by condensation thereof preferably comprise organic substituents consisting essen tially of monovalent organic radicals attached to silicon through carbon-silicon linkages, there being on the average between 1.95 and 2.25 organic radicals per silicon atom, and in which the siloxane units consist of units of the structural formula RzSiO where R is preferably a radical of the group consisting of methyl and phenyl radicals. At least per cent of the total number of R groups are preferably methyl radicals.
  • the polysiloxane may be one in which all of the siloxane units are (CH3)2SiO or the siloxane may be a copolymer of dimethylsiloxane and a minor amount (e. g., from 1 to 20 mol per cent) of any of the following units alone or in combination therewith: C6H5(CH3)SiO and (CsH5)2SiO.
  • the convertible organopolysiloxane may be compounded with various fillers on ordinary rubber compounding rolls, for example, silica, silica aerogel, titanium dioxide, calcium silicate, ferric oxide, chromic oxide, cadmium sulfide, asbestos, glass fibers, calcium carbonate, carbon black, lithopone, talc, etc., and molded, extruded, cast or otherwise shaped prior to the irradiation with the high energy electrons to give a product which after irradiation has physical characteristics, e. g., elasticity, compressibility, etc., similar to those of natural rubber and other known synthetic rubbers and Whose strength properties are comparable with those of silicone rubbers cured by means of chemical vulcanization accelerators and heat.
  • various fillers on ordinary rubber compounding rolls for example, silica, silica aerogel, titanium dioxide, calcium silicate, ferric oxide, chromic oxide, cadmium sulfide, asbestos, glass fibers, calcium carbonate, carbon black,
  • Fig. 1 is a partially sectionalized, simplified view of apparatus useful in the practice of the invention
  • Fig. 2 is a partially sectionalized view of alternative apparatus which may be employed to obtain, the desired results in accordance with the invention.
  • high voltage apparatus 1 capable of producing a beam of high energy electrons. for irradiating the convertible organ polysiloxane in accordance with the invention.
  • High voltage apparatus 1 may be of the type disclosed in United States Patent 2,144,518Westendorp, issued January 17, 1939, and assigned to the assignee of the present invention.
  • this apparatus comprises a resonant system having an open-magnetic circuit inductance coil (not shown) which is positioned within a tank 2 and energized by a source of alternating voltage to generate high voltage across its extremities.
  • a source of electrons which is maintained at the potential of the upper extremity of the inductance coil whereby a pulse of electrons is accelerated down envelope 3 once during each cycle of the energizing voltage when the upper extremity of the inductance coil is at a negative potential with respect to the lower end.
  • an elongated metal tube 4 the upper portion 5 of which is hermetically sealed to a tank 2, as illustrated, by any convenient means such as silver solder.
  • the lower portion 6 of. the tube 4 is conical in cross section to permit an increased angular spread of the electron beam.
  • End-window 7 which may be hermetically sealed to. tube 4 by means of silver solder. End-window 7 should be thin enough to permit electrons of desired energy to pass therethrough but thick enough to withstand the force of atmospheric pressure.
  • Stainless steel of about 0.002" thickness has been found satisfactory for use with electron energies of above 230,000 electron volts or greater because. this thickness of stainless steel stops electrons of lower energies. Beryllium and other materials of lower stopping power may also be advantageously employed.
  • endwindow 7 in arcuate shape as shown, greater strength for resisting the force atmospheric pressure may be obtained for a given window thickness. Desired focusing of accelerated electrons may be secured by a magnetic field generating winding 8 energized by a source of'direct current 9 through a variable resistor 9.
  • a platform 10 upon which the convertible organopolysiloxane 11 is positioned, is supported in the path of the electrons emerging from end-window 7 as illustrated.
  • High energy electrons penetrate the convertible organopolysiloxane (preferably containing a filler) to a depth dependent upon the energy of the electrons and density of the material, and thus initiate curing or vulcanization to form the solid, elastic, substantially infusible and insoluble products of the present invention.
  • Conversion of the organopolysiloxane to the vulcanized, solid, elastic state is essentially independent of the dose accumulation rate of electron irradiation but is dependent upon the total dose.
  • dose accumulation rate is meant the number of roentgen units of electron irradiation per unit time applied to the organopolysiloxane.
  • Total dose refers to the total number of roentgen units applied in the curing operation.
  • a roentgen unit as usually defined, is the amount of radiation that produces one electrostatic unit of charge per cubic centimeter of air under standard temperature and pressure conditions, and as employed here, refers to the amount of electron radiation measured with an air-equivalent ionization chamber at the position of the surface of the convertible organopolysiloxane.
  • the dependence of the cure upon total dose will be evident from the examples which are disclosed below.
  • the total dose may be varied depending on the degree of cure desired, and the depth of cure may be changed as desired by varying the energy level of the electron irradiation.
  • the actual degree of cure increases as the total dose is increased. In practice, it has been found that total doses of from about 2X10 roentgens (R) to 7 l0 R are desirable for most uses. However, total doses outside these limits may be employed where special applications are involved.
  • KVP refersto the peak voltage in kilovolts generated by the inductance coil with high voltage apparatus 1 during the conducting half cycle, and thus is a measure of the energy of electrons emerging from the window 7).
  • the irradiation dose was governed by the magnitude of the beam current, the position of the sample in the beam, and the length of time the sample was exposed to the beam.
  • the actual determination of the rate of accumulation of dose in R/sec. at the sample position in question was. determined by means of an air-equivalent ionization chamber. For example, in carrying out the tests described below, it was possible to realize a total dose of 2.5X10 R in 17.5 seconds at a distance of 10 cm. from the window of the accelerating tube with a beam current of microamperes.
  • the passage of the extruded composition through the beam was at a constant rate, this extrusion rate being fixed so that, for a particular beam current and location or position in the beam, the material remained exposed to the beam of electrons long enough to accumulate the total dose which was desired for curing.
  • EXAMPLE 1 In this example, essentially pure octamethylcyclotetrasiloxane was condensed at a temperature of about C. with 0.01 per cent, by weight, thereof KOH to give a highly viscous, substantially non-flowable, convertible polymeric dimethylsiloxane.
  • convertible organopolysiloxane was thereafter filled with various fillers, for example, silica aerogel, carbon black and lignin, and molded at room temperature into flat sheets and placed at about 10 cm. distance from the window of the apparatus described in Fig. 1 and irradiated with the high energy electrons.
  • the penetration of the electrons is directly proportional to the voltage and inversely proportional to the density of the material so that for a 3,000 kv. machine, total penetration is equivalent to about 13 mm. of water or for a density of 1.5, which is approximately that of the silicone rubber filled with silica aerogel, is about 9 mm.
  • machines operating, for instance, at voltages up to 3,000 kv. and about 10 milliamperes beam current it is possible to cure larger quantities of material and at a fast rate.
  • Threads of polymeric dimethylsiloxane containing the carbon black filler referred to above and free of any chemical curing agent have been extruded and passed by the exit window of the electron acceleration employed for effecting cure of the various silicone rubber composition-s described in Example 1, to yield a cured silicone rubber thread (0.030 diameter) which was cured as fast as it was being extruded.
  • the material was cured at a rate of about 0.6" per second and at a total dose of approximately 3X10 R using the apparatus described above.
  • EXAMPLE 2 100 parts of the convertible polymeric dimethylsiloxane described in Example 1 containing 50 parts, by weight, carbon black (Statex 93), was extruded in the form of a thin :wall tubing whose wall thickness was about 0.012" and outside diameter about A.
  • the tube was electron cured as it was being extruded at a rate of about 0.1" per second.
  • the average curing dose was about BXIO R.
  • the tubing was completely cured and was substantially infusible and insoluble.
  • chemical curing agents would be quite difiic-ult, especially since such thin wall tubing would normally collapse before complete cure could be effected.
  • This cured tube was quite heat resistant and even after many hours at elevated temperatures was extremely flexible.
  • Fig. 2 Continuous vulcanization of extruded convertible organopolysiloxanes may be obtained with apparatus such as that illustrated in Fig. 2 wherein similar numerals are utilized to identify like elements hereinbefore described.
  • the convertible organopolysiloxane 12 is extruded from an extruder 13 in the shape of the orifice of the die and continuously positioned upon a moving belt 14 which may comprise, for example, a continuous thin sheet of metal, such as stainless steel about 0.002" in thickness, extending around pulleys 15 and 16.
  • One of the pulleys may be connected to a driven shaft (not shown) so that the convertible organopolysilox-ane after being positioned upon the moving belt, passes under endwindow 7 as is indicated by arrow '17 and is irradiated by high energy electrons, and thereafter passes off the moving belt in the direction of the arrow at 18.
  • convertible organopolysiloxane may be produced containing, for instance, from 0 to about 150 per cent, by weight, filler based on the entire weight of filled material.
  • the filler (when used) on a weight basis may be employed in an amount equal to from about 0.15 to 3 parts of filler per part of convertible organopolysiloxane, for example, convertible polydimethylsiloxane.
  • the amount of such filler which may advantageously be used with the convertible organopolysiloxane is much less than usual fillers.
  • the amount of silica aerogel which may be tolerated in the filler composition is generally below 50 to 60 parts of the silica aerogel filler per parts of the convertible organopolysiloxane.
  • the rate of treatment that is, the dosage rate accumulation or the electron impingement rate, and the time of treatment or the rate at which the convertible organopolysiloxane has moved past the point at which irradiation is being carried out, etc., may be varied widely without departing from the scope of the invention.
  • Such products can be used as tapes which can be wrapped around, for instance, conductors, and thereafter subjected to further curing, for instance, electron irradiation, whereby the uncured portion is caused to become vulcanized in place using the wrapping force as means for pressure instead of using expensive molds for the purpose.
  • the presently described invention for rapid intermediate precures
  • convertible organopolysiloxanes containing curing agents e. g., benzoyl peroxide, etc, incorporated therein.
  • curing agents e. g., benzoyl peroxide, etc
  • the products of this invention are useful in applications, such as, for instance, tubing, electrical insulation (e. g., as conductor insulation, etc), shock absorbers, etc. They are particularly useful as gaskets in applications involving high temperatureconditions, especially in those places where they may be subjected to the effects of halogenated hydrocarbons as insulating media, namely, in the manufacture of capacitors. Because of their improved heat resistance, they are valuable as materials for use in applications where natural or other synthetic rubbers may fail owing to the deleterious effect of heat. Elastomers produced by the practice of our invention have the additional property of retaining their flexibility at low temperatures, for example, at temperatures as low as at least minus 60 C.

Landscapes

  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • Physics & Mathematics (AREA)
  • Oral & Maxillofacial Surgery (AREA)
  • Thermal Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Heating, Cooling, Or Curing Plastics Or The Like In General (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
US291542A 1952-06-03 1952-06-03 Vulcanization of silicone rubber with high energy electrons Expired - Lifetime US2763609A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
BE520402D BE520402A (enrdf_load_html_response) 1952-06-03
DENDAT1050993D DE1050993B (de) 1952-06-03 Verfahren zur Überführung von Polysiloxan in den festen elastischen Zustand
US291542A US2763609A (en) 1952-06-03 1952-06-03 Vulcanization of silicone rubber with high energy electrons
GB15194/53A GB757024A (en) 1952-06-03 1953-06-01 Improvements in and relating to the vulcanization of silicone rubber
FR1080171D FR1080171A (fr) 1952-06-03 1953-06-02 Vulcanisation des caoutchoucs de silicone par des électrons de grande énergie

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US291542A US2763609A (en) 1952-06-03 1952-06-03 Vulcanization of silicone rubber with high energy electrons

Publications (1)

Publication Number Publication Date
US2763609A true US2763609A (en) 1956-09-18

Family

ID=23120728

Family Applications (1)

Application Number Title Priority Date Filing Date
US291542A Expired - Lifetime US2763609A (en) 1952-06-03 1952-06-03 Vulcanization of silicone rubber with high energy electrons

Country Status (5)

Country Link
US (1) US2763609A (enrdf_load_html_response)
BE (1) BE520402A (enrdf_load_html_response)
DE (1) DE1050993B (enrdf_load_html_response)
FR (1) FR1080171A (enrdf_load_html_response)
GB (1) GB757024A (enrdf_load_html_response)

Cited By (57)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2900277A (en) * 1955-02-08 1959-08-18 Gen Electric Process of applying protective coatings by means of high energy electrons
US2907884A (en) * 1955-06-14 1959-10-06 High Voltage Engineering Corp Compact neutron source
US2914450A (en) * 1955-01-11 1959-11-24 Gen Electric Process for irradiating flat stock organic polymers
US2933441A (en) * 1957-10-14 1960-04-19 Astra Inc Process of making rubber articles
US2936261A (en) * 1955-05-18 1960-05-10 Gen Electric Sealing irradiated polyethylene
US2956904A (en) * 1954-11-04 1960-10-18 Minnesota Mining & Mfg Pressure-sensitive adhesive tapes
US2959531A (en) * 1956-08-01 1960-11-08 Phillips Petroleum Co Solid resins from irradiated epoxidized liquid conjugated diene polymers
US2959569A (en) * 1956-07-05 1960-11-08 Dow Corning Method of preparing organosilicon graft polymers
US2963747A (en) * 1957-05-15 1960-12-13 Western Electric Co Method of plastic encapsulation using irradiation
US2964457A (en) * 1957-06-28 1960-12-13 Phillips Petroleum Co Silica reinforced rubber
US2969327A (en) * 1958-07-23 1961-01-24 Du Pont Dielectric heat sealing blanket
US2975088A (en) * 1956-02-29 1961-03-14 Allis Chalmers Mfg Co Unsupported silicone rubber electrical insulation and method of preparing same
US2987431A (en) * 1956-08-31 1961-06-06 Buchler Franz Method of manufacturing panels and panel so produced
US2997418A (en) * 1956-10-18 1961-08-22 Gen Electric Cold welding of organopolysiloxanes
US2997419A (en) * 1956-10-18 1961-08-22 Gen Electric Cold welding of polyester resins
US3006830A (en) * 1957-05-31 1961-10-31 Dow Chemical Co Method for improving the dyeability of fiber-forming cellulose esters
US3007859A (en) * 1956-08-15 1961-11-07 Phillips Petroleum Co Atomic reactor
US3012001A (en) * 1957-03-06 1961-12-05 Us Rubber Co Composition of vinyl chloride polymer plus two unsaturated monomers
US3027312A (en) * 1958-05-29 1962-03-27 Phillips Petroleum Co Irradiation of tubular materials
US3037010A (en) * 1957-11-27 1962-05-29 Du Pont Polymeric perfluoro-2-butyne
US3056735A (en) * 1955-10-07 1962-10-02 S J Chemical Company Method of adhering cured silicone rubber
US3061001A (en) * 1958-09-12 1962-10-30 Zink Co John Gaseous fuel burner
US3061531A (en) * 1957-03-06 1962-10-30 Us Rubber Co Irradiation of vinyl chloride polymer plus two unsaturated monomers
US3061483A (en) * 1956-11-23 1962-10-30 Harold W Coles Coating of metal with layers of titanium esters and a polymer by exposure to high energy irradiation
US3065158A (en) * 1958-01-27 1962-11-20 Dow Corning Method of vulcanizing organosiloxanes
US3069378A (en) * 1957-08-16 1962-12-18 Gen Electric Covulcanizate of fluorinated polyacrylate elastomer and organopolysi-loxane gum
US3080990A (en) * 1961-03-10 1963-03-12 Vir Tis Co Inc Freeze-drying flasks
US3081485A (en) * 1958-11-20 1963-03-19 Steigerwald Karl Heinz Process and apparatus for treating synthetic plastic materials
US3090738A (en) * 1954-08-18 1963-05-21 Dow Corning Method of curing organosilicon compounds
US3098808A (en) * 1958-04-14 1963-07-23 Phillips Petroleum Co Promotion of high energy radiation effects in polymeric materials
US3123511A (en) * 1964-03-03 Radioactive treatment of insulating materials
US3144399A (en) * 1958-06-16 1964-08-11 Grace W R & Co Polyethylene product
US3158991A (en) * 1958-04-24 1964-12-01 Dal Mon Research Co Irradiated polymeric propellants and process of rocket propulsion
US3179546A (en) * 1958-12-03 1965-04-20 Dow Corning Method of bonding silicone rubber to other materials
US3203169A (en) * 1958-04-24 1965-08-31 Dal Mon Research Co Irradiated polymers and propulsion process
US3681786A (en) * 1970-07-13 1972-08-08 Medical Eng Corp Solid human prosthesis of varying consistency
US3807052A (en) * 1972-06-26 1974-04-30 Union Carbide Corp Apparatus for irradiation of a moving product in an inert atmosphere
US3959053A (en) * 1974-08-05 1976-05-25 The Goodyear Tire & Rubber Company Surface treatment of tires to reduce flash
DE2543514A1 (de) 1975-09-30 1977-04-07 Thagard Technology Co Verfahren zur durchfuehrung chemischer reaktionen bei hohen temperaturen, hierfuer geeigneter reaktionsapparat und dessen anwendung
US4158617A (en) * 1976-03-08 1979-06-19 General Motors Corporation Radiation cured and monomer modified silicon elastomers
US4362674A (en) * 1980-11-28 1982-12-07 High Voltage Engineering Corporation Process for making radiation cured silicone rubber articles
US4490314A (en) * 1980-11-28 1984-12-25 High Voltage Engineering Corporation Radiation cured silicone rubber articles
US4534889A (en) * 1976-10-15 1985-08-13 Raychem Corporation PTC Compositions and devices comprising them
US4737324A (en) * 1986-11-07 1988-04-12 Jmk International, Inc. Method of forming spark plug boots with radiation cure
US4775778A (en) * 1976-10-15 1988-10-04 Raychem Corporation PTC compositions and devices comprising them
US4865905A (en) * 1983-06-23 1989-09-12 Raychem Corporation Article for protection of a substrate
US5066755A (en) * 1984-05-11 1991-11-19 Stamicarbon B.V. Novel irradiated polyethylene filaments tapes and films and process therefor
US5466144A (en) * 1992-12-21 1995-11-14 Johnson & Johnson Vision Products, Inc. Apparatus for treating an ophthalmic lens mold
WO1996027430A1 (de) * 1995-03-04 1996-09-12 Gkss-Forschungszentrum Geesthacht Gmbh Strahlenchemisch modifizierte silikonkompositmembran für die ultrafiltration
EP1234846A4 (en) * 2000-06-15 2003-06-25 China Petroleum & Chemical SILICONE IN THE FORM OF FINE SULFIDE POWDER, PROCESS FOR PREPARING SAME AND APPLICATIONS THEREOF
US20110206924A1 (en) * 2008-10-29 2011-08-25 Liu Junkang J Electron beam cured, nonfunctionalized silicone pressure sensitive adhesives
US20110206923A1 (en) * 2008-10-29 2011-08-25 Liu Junkang J Electron beam cured silicone materials
US20110212325A1 (en) * 2008-10-29 2011-09-01 Determan Michael D Gentle to skin adhesive
US8822560B2 (en) 2008-10-29 2014-09-02 3M Innovative Properties Company Electron beam cured silicone release materials
WO2015143065A1 (en) * 2014-03-18 2015-09-24 Immunolight, Llc Improved adhesive bonding composition and method of use
US10087343B2 (en) 2007-08-06 2018-10-02 Immunolight, Llc Adhesive bonding composition and method of use
US10202721B2 (en) 2010-04-29 2019-02-12 3M Innovative Properties Company Electron beam cured siliconized fibrous webs

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4273634A (en) * 1979-11-14 1981-06-16 Dow Corning Corporation Precured silicone emulsion and method for preparation
FR2821865B1 (fr) * 2001-03-08 2003-08-15 Ferrari S Tissage & Enduct Sa Cable elastique tendeur

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB299735A (en) * 1927-05-30 1928-10-30 Hermann Plauson Process and apparatus for producing rapidly moving electrons and for subjecting matter thereto
US2350330A (en) * 1938-09-28 1944-06-06 Theron P Remy Treatment of hydrocarbons with radioactive materials
US2405019A (en) * 1943-10-05 1946-07-30 Plax Corp Process of making organo-silicon compounds containing a c-si bond
US2448556A (en) * 1947-01-16 1948-09-07 Gen Electric Synthetic elastic and elastomeric products
US2484595A (en) * 1947-01-16 1949-10-11 Gen Electric Synthetic elastic and elastomeric products
US2516848A (en) * 1945-10-09 1950-08-01 Electronized Chem Corp Method of producing butadiene from petroleum and petroleum fractions

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB299735A (en) * 1927-05-30 1928-10-30 Hermann Plauson Process and apparatus for producing rapidly moving electrons and for subjecting matter thereto
US2350330A (en) * 1938-09-28 1944-06-06 Theron P Remy Treatment of hydrocarbons with radioactive materials
US2405019A (en) * 1943-10-05 1946-07-30 Plax Corp Process of making organo-silicon compounds containing a c-si bond
US2516848A (en) * 1945-10-09 1950-08-01 Electronized Chem Corp Method of producing butadiene from petroleum and petroleum fractions
US2448556A (en) * 1947-01-16 1948-09-07 Gen Electric Synthetic elastic and elastomeric products
US2484595A (en) * 1947-01-16 1949-10-11 Gen Electric Synthetic elastic and elastomeric products

Cited By (65)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3123511A (en) * 1964-03-03 Radioactive treatment of insulating materials
US3090738A (en) * 1954-08-18 1963-05-21 Dow Corning Method of curing organosilicon compounds
US2956904A (en) * 1954-11-04 1960-10-18 Minnesota Mining & Mfg Pressure-sensitive adhesive tapes
US2914450A (en) * 1955-01-11 1959-11-24 Gen Electric Process for irradiating flat stock organic polymers
US2900277A (en) * 1955-02-08 1959-08-18 Gen Electric Process of applying protective coatings by means of high energy electrons
US2936261A (en) * 1955-05-18 1960-05-10 Gen Electric Sealing irradiated polyethylene
US2907884A (en) * 1955-06-14 1959-10-06 High Voltage Engineering Corp Compact neutron source
US3056735A (en) * 1955-10-07 1962-10-02 S J Chemical Company Method of adhering cured silicone rubber
US2975088A (en) * 1956-02-29 1961-03-14 Allis Chalmers Mfg Co Unsupported silicone rubber electrical insulation and method of preparing same
US2959569A (en) * 1956-07-05 1960-11-08 Dow Corning Method of preparing organosilicon graft polymers
US2959531A (en) * 1956-08-01 1960-11-08 Phillips Petroleum Co Solid resins from irradiated epoxidized liquid conjugated diene polymers
US3007859A (en) * 1956-08-15 1961-11-07 Phillips Petroleum Co Atomic reactor
US2987431A (en) * 1956-08-31 1961-06-06 Buchler Franz Method of manufacturing panels and panel so produced
US2997419A (en) * 1956-10-18 1961-08-22 Gen Electric Cold welding of polyester resins
US2997418A (en) * 1956-10-18 1961-08-22 Gen Electric Cold welding of organopolysiloxanes
US3061483A (en) * 1956-11-23 1962-10-30 Harold W Coles Coating of metal with layers of titanium esters and a polymer by exposure to high energy irradiation
US3012001A (en) * 1957-03-06 1961-12-05 Us Rubber Co Composition of vinyl chloride polymer plus two unsaturated monomers
US3061531A (en) * 1957-03-06 1962-10-30 Us Rubber Co Irradiation of vinyl chloride polymer plus two unsaturated monomers
US2963747A (en) * 1957-05-15 1960-12-13 Western Electric Co Method of plastic encapsulation using irradiation
US3006830A (en) * 1957-05-31 1961-10-31 Dow Chemical Co Method for improving the dyeability of fiber-forming cellulose esters
US2964457A (en) * 1957-06-28 1960-12-13 Phillips Petroleum Co Silica reinforced rubber
US3069378A (en) * 1957-08-16 1962-12-18 Gen Electric Covulcanizate of fluorinated polyacrylate elastomer and organopolysi-loxane gum
US2933441A (en) * 1957-10-14 1960-04-19 Astra Inc Process of making rubber articles
US3037010A (en) * 1957-11-27 1962-05-29 Du Pont Polymeric perfluoro-2-butyne
US3065158A (en) * 1958-01-27 1962-11-20 Dow Corning Method of vulcanizing organosiloxanes
US3098808A (en) * 1958-04-14 1963-07-23 Phillips Petroleum Co Promotion of high energy radiation effects in polymeric materials
US3203169A (en) * 1958-04-24 1965-08-31 Dal Mon Research Co Irradiated polymers and propulsion process
US3158991A (en) * 1958-04-24 1964-12-01 Dal Mon Research Co Irradiated polymeric propellants and process of rocket propulsion
US3027312A (en) * 1958-05-29 1962-03-27 Phillips Petroleum Co Irradiation of tubular materials
US3144399A (en) * 1958-06-16 1964-08-11 Grace W R & Co Polyethylene product
US2969327A (en) * 1958-07-23 1961-01-24 Du Pont Dielectric heat sealing blanket
US3061001A (en) * 1958-09-12 1962-10-30 Zink Co John Gaseous fuel burner
US3081485A (en) * 1958-11-20 1963-03-19 Steigerwald Karl Heinz Process and apparatus for treating synthetic plastic materials
US3179546A (en) * 1958-12-03 1965-04-20 Dow Corning Method of bonding silicone rubber to other materials
US3080990A (en) * 1961-03-10 1963-03-12 Vir Tis Co Inc Freeze-drying flasks
US3681786A (en) * 1970-07-13 1972-08-08 Medical Eng Corp Solid human prosthesis of varying consistency
US3807052A (en) * 1972-06-26 1974-04-30 Union Carbide Corp Apparatus for irradiation of a moving product in an inert atmosphere
US3959053A (en) * 1974-08-05 1976-05-25 The Goodyear Tire & Rubber Company Surface treatment of tires to reduce flash
DE2543514A1 (de) 1975-09-30 1977-04-07 Thagard Technology Co Verfahren zur durchfuehrung chemischer reaktionen bei hohen temperaturen, hierfuer geeigneter reaktionsapparat und dessen anwendung
US4158617A (en) * 1976-03-08 1979-06-19 General Motors Corporation Radiation cured and monomer modified silicon elastomers
US4534889A (en) * 1976-10-15 1985-08-13 Raychem Corporation PTC Compositions and devices comprising them
US4775778A (en) * 1976-10-15 1988-10-04 Raychem Corporation PTC compositions and devices comprising them
US4362674A (en) * 1980-11-28 1982-12-07 High Voltage Engineering Corporation Process for making radiation cured silicone rubber articles
US4490314A (en) * 1980-11-28 1984-12-25 High Voltage Engineering Corporation Radiation cured silicone rubber articles
US4865905A (en) * 1983-06-23 1989-09-12 Raychem Corporation Article for protection of a substrate
US5066755A (en) * 1984-05-11 1991-11-19 Stamicarbon B.V. Novel irradiated polyethylene filaments tapes and films and process therefor
US4737324A (en) * 1986-11-07 1988-04-12 Jmk International, Inc. Method of forming spark plug boots with radiation cure
US5466144A (en) * 1992-12-21 1995-11-14 Johnson & Johnson Vision Products, Inc. Apparatus for treating an ophthalmic lens mold
WO1996027430A1 (de) * 1995-03-04 1996-09-12 Gkss-Forschungszentrum Geesthacht Gmbh Strahlenchemisch modifizierte silikonkompositmembran für die ultrafiltration
EP1234846A4 (en) * 2000-06-15 2003-06-25 China Petroleum & Chemical SILICONE IN THE FORM OF FINE SULFIDE POWDER, PROCESS FOR PREPARING SAME AND APPLICATIONS THEREOF
US6838490B2 (en) 2000-06-15 2005-01-04 China Petroleum & Chemical Corporation Silicone rubber in the form of a finely divided powder, method for the production and the use of the same
US10087343B2 (en) 2007-08-06 2018-10-02 Immunolight, Llc Adhesive bonding composition and method of use
US8541481B2 (en) 2008-10-29 2013-09-24 3M Innovative Properties Company Gentle to skin adhesive
US20110212325A1 (en) * 2008-10-29 2011-09-01 Determan Michael D Gentle to skin adhesive
US20110206923A1 (en) * 2008-10-29 2011-08-25 Liu Junkang J Electron beam cured silicone materials
US8822560B2 (en) 2008-10-29 2014-09-02 3M Innovative Properties Company Electron beam cured silicone release materials
US8822559B2 (en) 2008-10-29 2014-09-02 3D Innovative Properties Company Electron beam cured silicone release materials
US9017771B2 (en) 2008-10-29 2015-04-28 3M Innovative Properties Company Gentle to skin adhesive
US9359529B2 (en) 2008-10-29 2016-06-07 3M Innovative Properties Company Electron beam cured silicone materials
EP2350220B1 (en) 2008-10-29 2017-04-12 3M Innovative Properties Company Electron beam cured silicone materials
US20110206924A1 (en) * 2008-10-29 2011-08-25 Liu Junkang J Electron beam cured, nonfunctionalized silicone pressure sensitive adhesives
US10202721B2 (en) 2010-04-29 2019-02-12 3M Innovative Properties Company Electron beam cured siliconized fibrous webs
US11001962B2 (en) 2010-04-29 2021-05-11 3M Innovative Properties Company Electron beam cured siliconized fibrous webs
WO2015143065A1 (en) * 2014-03-18 2015-09-24 Immunolight, Llc Improved adhesive bonding composition and method of use
US11345833B2 (en) 2014-03-18 2022-05-31 Immunolight, Llc Adhesive bonding composition and method of use

Also Published As

Publication number Publication date
BE520402A (enrdf_load_html_response) 1900-01-01
GB757024A (en) 1956-09-12
FR1080171A (fr) 1954-12-07
DE1050993B (de) 1959-02-19

Similar Documents

Publication Publication Date Title
US2763609A (en) Vulcanization of silicone rubber with high energy electrons
US2948666A (en) Irradiation process
US2921006A (en) Polymerization with high energy electrons
US3563870A (en) Melt strength and melt extensibility of irradiated linear polyethylene
Du et al. Dynamic behavior of surface charge on direct-fluorinated polyimide films
US2888419A (en) Polyethylene composition containing organopolysiloxane resin
US3179546A (en) Method of bonding silicone rubber to other materials
US3050490A (en) Boron nitride containing self-adhering
US3677877A (en) Article of silicone rubber having surfaces resistant to dirt pick-up
US2997419A (en) Cold welding of polyester resins
US3006463A (en) Self-fusing tape
Stelescu et al. Exploring the effect of electron beam irradiation on the properties of some EPDM‐flax fiber composites
US3050491A (en) Method of preparing self-adhering organopolysiloxane elastomers
US3084114A (en) Irradiated filler-containing polyethylene
US2904481A (en) Solid state polymerization
US3065158A (en) Method of vulcanizing organosiloxanes
US2997418A (en) Cold welding of organopolysiloxanes
US3116226A (en) Irradiation of fluorocarbon copoluymers
US2858259A (en) Electron irradiation of preformed polyamide resin
US4362674A (en) Process for making radiation cured silicone rubber articles
US2945792A (en) Polyolefins
US3056735A (en) Method of adhering cured silicone rubber
US2924559A (en) Polyethylene blend
US3090738A (en) Method of curing organosilicon compounds
US2979482A (en) Organopolysiloxanes stabilized with ferrocene and ferrocene derivatives